Coal partial combustion with pure oxygen



March 13, 1956 l.. c. PEERY ET AL COAL PARTIAL COMBUSTION WITH PURE OXYGEN 2 Sheets-Sheet l Filed May 29, 1950 GEORGE A.H|GKMAN 8 ALBERT E.H|R$CH ATTORNEY March 13, 1956 c. PEERY ET AL COAL PARTIAL COMBUSTION WITH PURE OXYGEN 2 Sheets-Sheet 2 Filed May 29. 1950 FIGII.`

FIGDI.

*v-WATER 30 FIGV.

lll/11111111 a MYNH ORAC 0 TEMS T N EKR @pcm A.. .m

2,738,263 COAL PARTIAL CoMBUsTIoN'wI'TH PURE OXYGEN Luther C; Peery, Charleston, George A.Hickman', Malden, and Albert E; Hirsch, Charleston, W. Va., assignors to E. I. du Pont Vde Nemours.& Company, Wilmington, Del., a corporation of Delaware Application May 29, 1'9'so,`seria1 N6; 165,018

7 Claims. (CLAS-206) This invention relatesto apfrocessior thepreparation of carbon monoxide and hydrogen by at least partial oxidation of commin'uted solid carbeiiaceous materials, and is more particularly directed to thepreparation of hydrogen, gaseous mixtures" containinghydrogen and nitrogen an'd gaseousmixtures containinghydrogen and carbon monoxide, by the partialoxid'ation of powderedcoai.

Many methods have'been proposed for the preparation ofisynthesis gasesof the abovecompesitions, although for all intents and purposesl vthe'ffuzisic'; sourceofjthese gases is coal, petroleumoils, ornaturalhgas. Synthesis gases are deriyed fromr these sourcesby pyrelysis, the coallirst is oo ked, then gasiled andthe petroleum hydrocarbons and natural gas cracked., Cracking of petroleurn oils for their synthesis' gas content is lineeonorlnicaln and this route is used only fof the utilizationofby-product gases. v In recentyears, natural gas and' gases higlrinhydroearbon content have been cracked Vto produce synthesis gasesfor reacted in accord with the hydrocarbon steam reaction to giye such gases. Theavailability,`however, ofhydrocarbon gases, whether naturalfor synthetic, haveisomewhat limited the extentfof this source.` Coal remains and will remain' for some time` the principal source, in spite yof the very` ineiiicient processes normally used for extracting gases. fr om coal. l v. y

'lo realize itssynthesisgas content, `coalpis usually subjected to destructive distillation in retorts, the 'distilled gas being subjected topuriiication forthe recovery ,principally of its hydrogen and olefin content; untreated the product gas has value onli/for its B t u content. The coke residue from the lretorts remains the principal source of synthesis gases, thehydrogen and carbon monoxide) being obtained from the coke byalternate heating'withairand blasting with steam,l the `purified gaseslfrom the' steam run beingused the synthesis of ammonia, alcohol and other organic compounds,` z Y h?. Cake @van :route te the rfrafatige Of a Synthesis is vanreinstalloi-rawmateral and wasteful f the haar Cftitsnt 0f the sosl- ,Prqcesses havey b-@e' ,proposed whereby such gasesare deriveddirectlyfrom coal with- Qu APassing Atherein the oude; destructive distillation proc s ses. `Ognly a single p rocess, howeve r, theWinkler pijocess, operated` forl ,a Ashort `time on brown coal in Oppau, `iermany, appears tohavensed this route commerciallig Thisv prpcessuinvolyed .introducing oxygen andstearn `intoafixed,f luidized bed ofiinefuel, the bed acting rnuch`lilea liquid. in the boiling. state. .The ,agitation .of the particles within the bed was maintained by the flow of gases ,through' the` bed. Operation of such a process, however, is difficult for care mustbe exercised in theI controlof gas velocities to maintain the bed in a tluidizedstate, otherwise blow holes form and unreacted oxygen passes the bed causing explosions, roughoperation and local damage. Difficulties andl ineiciencies also arise from excessive fuel carry-over in the product gas.' No' comin'ercially'u acceptable process; accordingly, iseiitat'in"th`eUnited States'Y in' which synthesis gases United States Pat'tt C icc t 2 containinglow inerts and lowmethane concentrations are produced directly from coalwithout passing through the costly destructive distillation step incoke ovens.

An object o f thepresentinvention is toprovidetan improved process for the preparation of synthesis gas mixtures from coal.y Anotherobject is"to` provide a process for the preparation, of gases containing principally hydrogen, carbon monoxide and hydrogen, or hydrogen and nitrogen, wherein the purityand/ or the ratio of constituents can be accurately controlled. A further object is to provideafprocess for the partialcombustion' ofsolid carbonaceous fuels, such as powderedcoal,l bya simplemand highly etlicient process. Yet anotherobjectis to provide a method of conducting,suchprocesses.sealed from the atmosphere, Other objects and/advantages of `the invention will hereinafter appear, and will he more fully understood by reference to the lspecification and ,to theaccompanyingy drawings 4which diagrammatically illustrate a preferred form andassemblage of apparatus in which the reactionv tales pl ace t lThe invention is directed principally to an improved method of supplying crushedor powdered coal to the partial oxidation of coal in s team to the oxides of carbon and hydrogen. VThisis `realized bylproviding a pressure sealorheadrof crushedor powdered coal, similar/to a hydraulic` head, by means o f whichbackward leakage of supeheated steam from theprocess is avoided andgco'ntinuous feeding Aof the coalufrom a zone at essentially atmospheric pressure toa higher pressure zone, e. g.I '3 pounds per` square ,inch gau geor higheris made possible.

The invention, will4 ,be 4nnte readily' understood by referencetoy the drawings in which like parts have like numbers throughout.` i'

Fig-L lilltlffas? all aPPaUlS. in which4 111@ process .0f theinvention is carried out, and in which coal ispulverized, then lsuspended in superheatedsteam, which suspension 'isf thoroughly with oxygen, or oxygen fortified air', andl the resulting ,mixture subjected to partial comb1` 1`s'tio1 i.`= The gaseofusproducts Iaire, separatedfrom the slagandiash produced' during lthe partial combustionof the powderedfcal, andthen are treated for the-prepara. tiono'f'a gasmof'hy gen, of hydrogen and carbonv Inonoxide, (ii-"ofjhydiogen andnit'rogen. At the higher en,d of fthe op@ 'fi'r'iatnpeitl ',riise essentially all .Of .the ash, content' of, -the",ceal` is removed from the furnace as liquidslag. A The series of operations illustrated provide an .Overall process ,foi". Producing aV highly, eicient and economical conversion' of Ithe volatile matterand ixed c'a'rbori'in a l,`, Vation productsilogether with der produc of ste'amf'to synthesis gas mixtures.

I iig, i," diagrammatically illustrates Vapparatus that may be used," Conveyer 1 transports coal in to hopper 2 of a hamrriefhmilliwhereianylumps of coal are crushed. Fronilhammermilli the"cru shed'c'oal drops into bunker 4,V f roni'the botto' of which' iriftu'rnithe crushed coal is fed byygravity toweighing'hoppersf Fromtheweighing h OPPCr 5 thecoalpasses'into thep'ortion of the apparatus whichislaprincipal'fea e of the invention and which is illustratedmo're in detailin Fig, VIII.v In' Fig; Villis illustrated diagrammatieally an `apparatus for sealing the pulveriz'er and apparatus associated therewithy (which will be more fully particulariied'hereinafter) by crushedor powdered coal'to maintain a pressure head of coal whereby, inter alia, the steam usedfinfpulverizing the coal, is prevented from backing up into the coal supply. The backing upof steam results in condensation of steam in the crushed or powdered coal, wetting ofthe coal, and intermittent bridging and flow stoppage in the coal feeder pipes. A coal seal leg 61 is fed with crushed or powdered.. coal from weighingliopper Sthrough the rotary'dis'charge' gate 64, the coal seal 'leg'being open" to the atmosphere' around the periphery of the funnel shaped top 63. Dry pressurized air at 2 to 10 pounds per square inch absolute, or other dry gas such as nitrogen, carbon dioxide or natural gas, is introduced into the coal seal leg 61 through ports 65 to maintain the crushed or powdered coal in a semi-fluid or Huid state and to augment the seal by this air. The powdered coal and some air is discharged through the rotary seal valve metering device 62 into the screw feeder 6. Through port 66 carbon dioxide or other inert gas, similar to those described above, may be introduced when required to dislodge any jams or bridging that may occur.

The coal seal leg 61 is kept substantially filled with crushed or powdered coal and provides a back pressure by the uid column of crushed or powdered coal and air in the leg. This head offsets the back pressure of the feeding and pulverizing mechanism in the train following the leg. The creation of a suicient back pressure in the coal seal leg 61 also eliminates the necessity of using the coalsteam blower 9 which may be by-passed entirely during normal operation of the process. Blower 9, because of the superheated steam and coal particles, corrodes and erodes rapidly requiring frequent repair. The installation of the coal seal leg 61 avoids the need for this apparatus for the pressure head overcomes the back pressure otherwise built up in the system.

A coal meter 67 provided with a no coal alarm not shown, measures the flow of coal by means of the rotary feeder 68. The gas introduced into the coal seal leg 61 in addition to maintaining a static head on the system, uidizes the powdered coal, the excess gas being discharged at the top of the seal pipe 63. The gas ow rate into ports 65 should be ample to produce a superficial velocity of 0.1 to 0.3 feet per second up through the coal in the seal leg 61. Under these conditions a static sealing pressure of 8 inches to l0 inches of water will be developed per foot of seal length; with a 7.5 foot seal leg length a pressure of 2 to 3 p. s. i. g. can be held in the pulverizer 8.

The coal from the seal leg 61 and rotary seal metering valve 62 passes into a device 6 with screw feed 7 which forces the measured portion of the crushed coal into a steam pulverier 8 wherein the crushed coal is comminuted and the product picked up by steam which transports it as a steam-coal fluid stream into high velocity jet burner 10 or 10a, burner 10 being directed axially and downwardly into theqgas generator 12, and burner 10a being directed tangentially into the upper section of the generator 12. In burner 10 the steam-coal mixture is combined with oxygen of at least 90% purity which is forced into the burner by blower 11. The coal-steam-oxygen mixture issues from burner 10 into gas generator 12 in which the mixture of gases is ignited. The gaseous products of ignition ilow from gas generator 12 through conduit 13 to wash box 14, the washed gases issuing from wash box 14 through conduit 15 and gas cooler 16 to a suitable gas holder not shown. The slag produced in gas generator 12 flows through a tapping hole 17 provided in the bottom of the gas generator 12 and drops into the water held in quench tank 18. The tapping hole 17 may, if desired, be located in the wall at the side rather than at the bottom of the generator 12 as shown, and may vary between about 1/50 to 17400 of the furnace cross-section. The port of the tapplng hole 17 is kept hot and free of slag plugs by withdrawing from about 10 to 25% or more of the product gas through this port. This hot gas may, if desired, be passed through the stem superheater 21 to preheat the entering steam and/or returned to the main product gas stream via an auxiliary blower not shown. From the bottom of quench tank 18 the slag is lifted by means of conveyer 19 to slag hopper 20. Steam is introduced into the system for superheater 21 from which it is passed into the pulverizer 8 and, if desired, may be introduced 1 nto the steam entrained coal. Cooling water is sprayed luto the generator gases at 22 Loriot to passing them into 4 the wash box 14. A flare stack 23 and valve 24 are provided for discharge of the gases produced during start-up, shut-down or control during periods of unsteady operation.

Figs. ll and III illustrate, in detail, the construction of the high velocity jet burners 10 and 10a in which the steam-coal suspension from one arm 30 of the burner meets the oxygen from the other arm 31 in the mixing chamber 32. The material 0f construction of mixing chamber 32 is preferably stainless steel tubing or other metal resistant to high temperatures, chamber 32 being encased in castable re brick refractories 33 and 34. A water jacket 35 on the mixing chamber 32 is desirable to prevent fusion of the tip when the hot furnace is shut down.

The hammer mill is adjusted to crush the lump coal to a size of 1A or less, and this crushed Coal is then dropped into the pulverizer 8 wherein it is ground to a product approximately or more of which will pass through a 200 mesh U. S. standard screen. Any suitable type of mechanical pulverization may be used. The known commercial steam jet type pulverizers are especially well adapted for this particular operation because the pulverized coal after grinding is entrained in steam substantially at one and the same time, and passed from the pulverizer as a steam-coal fluid mixture, the coal being suspended by a suicient quantity of steam flowing at a suicient velocity to carry the coal to the burner.

One manner of removing the slag from converter 12 is illustrated in Figure l. In the apparatus illustrated by this gure the slag falls by gravity through tapping hole 17 into a liquid, which may be water or any other suitable quenching medium, in quench tank 18. The molten slag, as it is quenched in the liquid, solidies and is picked up by the conveyer 19 and discharged into the slag hopper 20.

Continuous iiow of slag through tapping hole 17 is essential to successful operation of the process. Without some means of maintaining this flow by keeping this hole open, How of the molten slag into conduit 13 may result in plugging of the apparatus. With many types of coal the temperature of the slag is close to its freezing point and there is a tendency to plug even with a slight lowering in temperature within the generator. Plugging, however, is avoided, as described, by passing a relatively small portion of the hot product gases through tapping hole 17 to maintain the slag passing through this aperture above its solidication temperature. The product gases may be removed from the free space above the quenching liquid and discharged into conduit 13, 15 or used for superheating steam or for any other desired purpose. Water, if used for quenching, is generally at its boiling point; considerable steam is formed and is withdrawn with the hot gases through the exit pipe 40.

Figure IV illustrates a modied product gas and slag separating unit situated at the bottom of the generator 12. The product gas flows down through generator 12 and through slot 41 into the slag discharge chamber 42. From this chamber the product gases rise and pass from generator 12 through conduit 13. Slot 41 discharges the product gas tangentially into chamber 42, the centrifugal force of which aids in removal of incandescent dust particles. The molten slag likewise ows into chamber 42 through the lower part of slot 41 catching the particles as they are forced outward and downward. Fig. V is a cross section at A-A of Fig. 1V giving the positions more in detail of the slot in this type of apparatus. The slag, as in the detail shown in Fig. l, passes through tapping hole 17 with a portion of the product gas which is discharged from the generator 12 through conduit 40, the molten slag falling directly into the liquid in a quench tank such as that shown in Fig. I.

It is not essential that the tapping hole 13 be positioned on the center line of the generator but may be situated of center and preferably situated at the hottest part of the discharge end of the generator 12 to insure that the molten slag be dischaged as a iluid.

There is a tendency for the molten slag, as it passes through the tapping hole 17 to solidify before it is quenched and to build up on the periphery of the tapping hole 17. This is due in part to radiation of heat to the quenching liquid. The relatively small ratio of molten slag radiating to the water is a feature of the invention that inhibits plugging. Lip 43, Fig. VI, also inhibits to a large extent solidifcation and build-up of slag around the hole. Lip 43 is constructed and. mounted in such a way that it can be readily removed and replaced without materially disturbing the rest of the generator lloor. A removal door 45 is provided to permit examination of the generator floor and, if necessary, permits rodding to break up undesirable slag formation.

The generator 12 is lined, as is also the oor 44, with a suitable type of fire brick.

To start the reaction, gas generator 12 and auxiliary piping are brought up to temperature by burning natural gas or other fuel introduced into the high velocity jet burner at 27. This fuel is mixed with oxygen or air and burned within the generator 12 until the generator reaches a uniform temperature of about 1000 C. to 1200 C. When this temperature has been attained, coal and steam are introduced into the fuel stream and the ratio of steam-coal suspension gradually .increased over a period of about an hour, at the end of which time substantially all auxiliary fuel ow is cut oi. Commencing operation in this manner minimizes explosion hazards in gas generator 12. During normal operation of the process, the temperature within the combustion zone is held above l200 C. and preferably above l400 C., the maximum temperature at the chamber wall being between l300 and l700 C., the temperature being adjusted inter alia by control of rates of oxygen and coal injection. Flash-back of the flame into the burner is avoided providing a high uid velocity is maintained in the jet burner at all times. This velocity should be 100 feet per second for nozzles having diameters up to 3% with velocities of at least 150 feet per second and preferably above 300 feet per second for larger nozzles. During the start-up period and after the interior temperature of the generator 12 has reached 1200 C. and the fuel is slowly replaced by the steam-coal mixture, a complete replacement is effected without hazardous flash-back difculties, if the proper' velocities are maintained.

Figure VH illustrates diagrammatically and in crosssection another method of discharging the slag and the product gas from the generator 12. ln this modification it ispreferable to introduce the coal-steam-oxygen mixture tangentially into the generator 12 through the burner 10, the slag swirls spirally down into the annular space 50 surrounding the product gas exit 13, the slag being discharged through slag port 17 into a quenching tank similar to that illustrated in Figure I. By the tangential introduction of the coal-steamroxygen mixture into the generator 12 the slag is driven centrifugallyagainst the outer walls of the generator which is preferably circular and flows, out of intermingling contact with the productgases, into the annular space 50.

The partial combustion of the lcomminuted coal may be operated with either up-ilow, down-flow or side-flow of the steam-eoal-oxygen mixture into the gas generator 12. Down-ow, as illustrated, either in axial or tangential direction, is preferred since it has been found that the temperatures throughout the length of the furnace are more nearly equal when the ow is in this direction, while a very short, high temperature zone may be `encountered in an up-i'low operation. Slag removal problems are also minimized with down-flow operation. The steam has a tive-fold function to perform; iirst, to pulverize the coal in steam pulverizer; second, to transport the coal as an entrained stream from the pulvering to the high velocity jet burner.

izer tothe high velocity jet burner; third, to provide an incipient distillation of'volatile material from the coal; fourth, to limit and control the reaction temperature; and fifth, to serve as a reactant in the process. It s essential that the coal-steam mixture be maintained after comminution above the dew point of its moisture content in order to prevent precipitation within the conduits lead- When operating at temperatures only slightly above the dew point, the optimum advantages of the process are not realized, for it has been found that` if the steam temperature is increased to a temperature above that at which incipient distillation of volatile materials from the coal occurs, this distillation facilitates ignition andsubsequent partial combustion of the coal. As is well konwn, most bituminous coals reach a plastic state at a temperature of about 400 C., in which state the coal is quite sticky and difficult to transport without clogging of equipment. As a consequence, the steam-coal stream is preferably maintained at a temperature between 200 and 400 C., and preferably between 250 land 350 C.

To insure suicient steam to carry the coal, the amount of steam should range between 0.5 to 1.5 pounds' per pound of coal, depending to a large extent upon the height necessary to carry and to lift the coal from the pulverizer to the burner and on the resultant velocities in the transport lines. The steam supplied to the pulverizer should be underv a pressure between and 150 p. s. i. g., and preferably between 100 and 120 p. s. i. g., the blowers 9 [and/or coal seal leg 61], 11 and 25 operating to deliver iuid-sat pressures between 1.0 and 5.0 p. s. i. g. Auxiliary steam in excess of pulverizer requirements may be supplied, if desired, at low pressure between 5 and 10 p. s. i. g.

One of the outstanding features of the invention rests in the prernixing of the steam-coal suspension with oxygen prior to partial combustion of the Vcoal content of the mixture. Mixing chamber 32 is so designa-ted, with respect to length yand cross-sectional area, and the steamcoal suspension entering the chamber simultaneously with the oxygen at such velocities, that the combining fluids set up a high degree of turbulence within the chamber, whereby thorough and uniform mixing is accomplished. To attain this result the `chamber should have a length of at least 25 chamber diameters.

The oxygen introduced into the burner should be' of not lappreciably less than purity, preferably 4above purity, and is used in suiiicient amounts to give steam-oxygen mixtures containing from 25 to 50 (mol percent) oxygen, and preferably from 30 to 40 (mol percent) oxygen based on the steam-oxygen mixture. Many factors such as fuel composition-s and relative proportions of coal and steam influence the amount of oxygen required. With constant steam and coal flow-s, an increase in oxygen over that stoichiometrically required decreases the hydrocarbon leakage, increases the furnace temperature and reduces the vHz/CO ratio in the product gas. It has, likewise, been found that loss of heat through combustion chamber walls increases inordinately the excess oxygen requirement, and conversely preheating the inlet gas and powdered fuel decreases the oxygen requirement for maintaining the hydrocarbon leakage essentially -at zero.

If desired, steam or nitrogen (as pure nitrogen or flue gas) may be introduced at any point such, for example, as through auxiliary inlet 26 into the ignited gas in the generator 12 in order lto lower the combustion temperature and act to quench the product gases. If steam is introduced, it, at one and the s-ame time, increases the hydrogen content of the gas due to the decomposition of steam in accord with the water gas reaction and the hydrocarbon steam reactions which take place. While the temperature is not optimum for `these reactions, nevertheless, it appears that they do occur, even under these rather unfavorable conditions. Nitrogen may be introduced at such point to give a nal nitrogen containing gas and also to cool the combustion gases. Whether thesteain is introduced in la. single stream with the powdered fuel or partially with the fuel and partially into the converter itself, the same overall ratio of steam to powdered fuel should be maintained, lf desired, the product gas containing nitrogen can be produced 'by using air introduced by air blower 25 into the oxygen. The air diluted oxygen mixture is combined in the high velocity jet burner 10 with the steam-coal stream. To produce a product gas for use in the synthesis of ammonia, the oxygen is diluted with air in an amount sulicient to give a product gas containing a hydrogen to nitrogen ratio of about 3. inasmuch as the nitrogen content of the air introduced on a weight basis is the same as that found in the product gas, simple stoichiometric calculations will determine the optimum ratio of air to coal to be employed to give the desired nitrogen content in the product gas, whether the nitrogen be introduced via air, ue gas, or other nitrogen carrier, or into whatever part of the system the nitrogen or nitrogen carrier gas is introduced. Some small amounts of nitrogen will at times be introduced with the commercial oxygen and hydrocarbonaceous fuel, and this, of course, should be considered in the calculations.

If steam is to `be used to quench the product gas and increase the Hz/CO ratio, it is preferably used in a steam to coal weight ratio ranging between 0.1 to about 1.0, and preferably between 0.2 and 0.5. This will decrease the `furnace temperature at the point of steam addition, and likewise produce a gas containing a higher ratio of hydrogen to carbon monoxide.

In the table which follows preferred embodiments of the process of the invention are further exemplified. The combustion vessel used in operating in accord with the processes of the table comprise a furnace shell of 2 superimposed and lined cylindrical sheet steel sections bolted together, each about 4 feet high with a 42 inch outside diameter and a l2 inch inside diameter. The reaction zone had a refractory 4 inch inside lining of silicon carbide, a refractory 4 inch layer made of Alfrax alumina brick, `and between this refractory and the steel shell a four 'inch layer of Armstrong A-ZS insulating brick and a 3 inch `layer of Firecrete castable insulation. The burner jet consisted of a 11/2 inch stainless steel throat 32 with the arms 30 and 31 of the burner being constructed of 11/2 inch and one inch stainless steel pipes respectively, pipe 32 being encased in a refractory 33 and water cooled with the indicated jacket.

T he apparatus was operated at an average rate of about 3 to 4 pounds of powdered coal introduced per minute, with 100 to 185 standard cubic feet per minute of product gas produced per square foot of cross-sectional area, and a maximum throughput of about 200 cubic feet per minute per square foot. The inside refractory temperature averaged about l500 C. at which temperature no serious refractory fusion occurred.

of ammonia, in which a gaseous mixture of carbon monoxide and hydrogen is used; or to prepare it for use in the synthesis of ammonia, in which a gaseous mixture of nitrogen and hydrogen is used; or to prepare it for use as a hydrogenation gas in which only its hydrogen content is used. Known methods may be used for treating the gaseous mixtures to give such synthesis gas mixtures or a process used such as that described in the co-pending application of L. C. Peery and R. H. McKane, S. N. q7.614, filed July 8, 1948, now abandoned.

We claim:

l. In a process for the preparation of carbon monoxide and hydrogen by partial oxidation of comminuted carbonaceous material in a combustion Zone with steam and highly concentrated oxygen, the steps which comprise maintaining the comminuted carbonaceous material in the form of a tluidized column of crushed solids exerting a pseudo hydrostatic pressure at the base thereof, passing the crushed solids from the base of said column into suspension with steam while pulverizing the crushed solids, adding highly concentrated oxygen to said suspension, then injecting the constituents of the suspension into a reaction zone as a unitary combustion flame to form carbon monoxide and hydrogen and maintaining a pressure at the base of said column which is greater than that in the crushed solid-steam suspension.

2. In a process for the preparation of carbon monoxide and hydrogen by partial oxidation of comminuted carbonaceous material in a combustion zone with steam and highly concentrated oxygen, the steps which comprise maintaining the comminuted carbonaceous material in the form of a fluidized column of crushed solids by a dry inert gas, the column exerting a pseudo hydrostatic pressure at the base thereof, passing the crushed solids from the base of said column into suspension with steam while pulverizing the crushed solids, adding highly concentrated oxygen to said suspension, then injecting the constituents of the suspension into a reaction zone as a unitary combustion ame to form carbon monoxide and hydrogen and maintaining a pressure at the base of said column which is greater than that in the crushed solid-steam suspension.

3. The process of claim 2 in which the dry inert gas is carbon dioxide.

4. In a process for the preparation of carbon monoxide and hydrogen by partial oxidation of comminuted coal in a combustion zone with steam and highly concentrated oxygen, the steps which comprise maintaining the comminuted coal in the form of a uidized column of crushed solids exerting a pseudo hydrostatic pressure at the base thereof, passing the coal from the base of said column into suspension with steam while pulverizing the coal, adding highly concentrated oxygen to said Table I Percent S Tllasts Bureau of Mines Analysis-Product Gas, o en Steam Coal, as Oxygen gleam Chamber percent Runs c gm f lbs /mi fed, in Steam, M.

ibs/nun o, Mixm' une 'QFOCDI Ptl'a H, oo oo, 0. N. 111. CH.

33. 0 3. 2 3. 65 34. 1 125 1, 535 1, 430 30. 1 37. 9 22. 3 0. 2 8. 9 0. 3 0. 3 30. 5 3. 1 3. 04 33. 0 105 l, 550 1, 420 35. 3 40. 6 17. 1 0. 3 6. 0 0. 2 0. 5 25. O 3. 1 2. 47 28. 8 13() 1, 500 1, 400 34. 9 39. 5 19. 3 0. 2 5. 5 0. 2 0. i 25. 0 2. 9 2. 56 30. 2 125 1, 485 1,390 34. 8 38. 6 20. 5 0. 2 5. 5 0. 1 0. 3 35. U 3. 0 3. 66 36. 9 115 1, 500 l, 440 32. 3 41. 1 15. 2 0. 0 8. 6 2. 1 0. 4 37. 0 3. 1 3. 7G 37. 5 100 1, 510 1, 430 35. 1 43, 5 15. 7 0. 2 4. 9 0. 2 0. 4

The product gas obtained by the partial oxidation of the pulverized fuel may be used directly after its withdrawal from the gas cooler 16, or may be further treated in order t-o prepare it for use in the synthesis of methanol, in which a gaseous mixture of carbon monoxide and hydrogen is used; or to prepare it for use in the synthesis suspension, then injecting the constituents of the suspension into a reaction zone as a unitary combustion llame to form carbon monoxide and hydrogen and maintaining a pressure at the base of said column which is greater than that in the coal-steam suspension.

5. The process of claim 4 in which the coal is maintained in suspension in the uidized column by a dry inert gas.

6. The process of claim 5 in which the dry inert gas is carbon dioxide.

7. In a process for the preparation of carbon monoxide and hydrogen by partial oxidation of comminuted coal in a combustion zone with steam and highly concentrated oxygen of atleast 95% purity, the steps which comprise maintaining crushed coal of less `than 1A inch diameter in the form of a udized column of solids exerting a pseudo hydrostatic pressure at the base thereof, passing the coal from the base of said column into a pulverizer to comminute the major portion of the coal to pass through a 200 mesh U. S. standard screen, and into suspension with the said steam while pulverizing the crushed solids, adding oxygen of at least 95 purity to said suspension, then injecting the constituents of the suspension into a reaction zone as a unitary combustion flame to form carbon monoxide and hydrogen, and maintaining a pressure at the base of said column which is greater than that in the coal-steam suspension.

References Cited in the ile of this patent UNITED STATES PATENTS 1,924,856 Heller Aug. 29, 1933 2,304,827 Jewell Dec. 15, 1942 2,568,400 Kearby Sept. 18, 1951 2,577,632 Roetheli Dec. 4, 1951 2,579,398 Roetheli Dec. 18, 1951 2,614,915 Hirsch 1 Oct. 21, 1952 2,619,449 Sweetser n- Nov. 25, 1952 2,623,817 Lewis Dec. 30, 1952 OTHER REFERENCES Yellot: National Engineer, June 1946, pages 448- 454.

Schmidt et al.: Chemical Engineering Progress, October 1948, pages 737-744.

Albright et al.: Chemical Engineering, June 1949, pages 10S-111.

Bureau of Mines: Report of Investigations 4651, February 1950, pages 57--59 and Figure 76. 

1. IN A PROCESS FOR THE PREPARATION OF CARBON MONOXIDE AND HYDROGEN BY PARTIAL OXIDATION OF COMMINUTED CARBONACCOUS MATERIAL IN A COMBUSTION ZONE WITH STEAM AND HIGHLY CONCENTRATED OXYGEN, THE STEPS WHICH COMPRISE MAINTAINING THE COMMINUTED CARBONACCOUS MATERIAL IN THE FORM OF A FLUIDIZED COLUMN OF CRUSHED SOLIDS EXERTING A PSEUDO HYDROSTATIC PRESSURE AT THE BASE THEREOF, PASSING THE CRUSHED SOLIDS FROM THE BASE OF SAID COLUMN INTO SUSPENSION WITH STEAM WHILE PULVERIZING THE CRUSHED SOLIDS, ADDING HIGHLY CONCENTRATED OXYGEN TO SAID SUSPENSION, THEN INJECTING THE CONSTITUENTS OF THE SUSPENSION INTO A REACTION ZONE AS A UNITARY COMBUSTION FLAME TO FORM CARBON MONOXIDE AND HYDROGEN AND MAINTAINING A PRESSURE AT THE BASE OF SAID COLUMN WHICH IS GREATER THAN THAT IN THE CRUSHED SOLID-STEAM SUSPENSION. 